Cationic polymeric fluorinated ether silane compositions and methods of use

ABSTRACT

A polymer is provided comprising a first pendant group selected from at least one of a perfluorinated ether group or a perfluoroalkanesulfonamido group, a second pendant group comprising an ammonium group, wherein the second pendant group is free of silicon, and a third pendant group comprising an ammonium group and a reactive silicon-containing group. A composition comprising the polymer is provided. The polymer and composition are useful for protecting a substrate, for example, to render the substrate oil repellent, water repellent, or both, or to provide stain repellency to the substrate.

TECHNICAL FIELD

The present invention relates to cationic polymeric fluorinated ethersilane compositions and methods of using these compositions.

BACKGROUND

Some fluorinated compounds can impart water and oil resistance tosubstrates such as, for example, textiles, paper, non-woven materials,leather, and masonry. Water and oil resistance has been achieved byapplying a composition comprising a fluorinated compound to, forexample, the surface of a substrate. Fluorinated compounds that havebeen shown to impart water and oil resistance to substrates include somepolymeric fluorinated compounds, i.e., fluorinated polymers. Fluorinatedpolymers include polymers having fluorinated groups pendant to a polymerchain, for example, fluorinated (meth)acrylate polymers and fluorinatedurethane polymers.

In many cases, the fluorinated compounds have been applied to thesurface of a substrate in a composition comprising a substantial amountof an organic solvent. In some cases, the organic solvent has comprisedchlorine- and/or fluorine-containing compounds such astetrachloroethylene or trichlorotrifluoroethane. Methods to apply asolution of a fluorinated compound have included spraying the solutionfrom a pressurized container such as an aerosol can.

SUMMARY

There is a need for compositions comprising fluorinated polymericcompounds, particularly cationic polymeric fluorinated compounds, thatcomprise or can be delivered from aqueous or substantially aqueous mediaand that can impart water and oil resistance to substrates and, moreparticularly, to surfaces of substrates.

In one aspect, a polymer is provided that comprises a first pendantgroup selected from at least one perfluorinated ether group orperfluoroalkanesulfonamido group, a second pendant group comprising anammonium group, where the second pendant group is free of silicon, and athird pendant group comprising an ammonium group and a reactivesilicon-containing group.

In another aspect, a polymer is provided, the polymer prepared fromreactants comprising a first monomer having the structure of Formula I

a second monomer having the structure of Formula II

a first quaternizing agent comprising at least one acid or silicon-freealkylating agent, and a second quaternizing agent comprising thestructure of Formula IIIX—R⁶—Si(R⁷)₃.  (III)In Formula I, R_(f) is selected from a structure of Formula IVF(C_(m)F_(2m)O)_(n)C_(p)F_(2p)—,  (IV)where m is an integer of 1 to 12, n is an integer of 1 to 20 and p is aninteger off 1 to 6, a structure of Formula VC_(x)F_(2x+1)SO₂N(R¹)—,  (V)(where x is an integer of 1 to 6 and R¹ is a hydrogen atom, an alkylgroup, an aryl group, or an aralkyl group), and combinations thereof. InFormula I, group A is a linking group having less than 11 carbon atoms,and R¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.In Formula II, R² comprises at least one of an alkylene group, aheteroalkylene group, an arylene group, or an aralkylene group, each R³is independently a hydrogen atom or an alkyl group, and R¹¹ is ahydrogen atom or an alkyl group having 1 to 4 carbon atoms. In FormulaIII, X is a leaving group selected from halo, alkyl sulfonate,fluorinated alkyl sulfonate, aryl sulfonate, and fluorinated arylsulfonate, R⁶ is an alkylene group having less than 11 carbon atoms, andeach R⁷ is independently a hydroxy group, an alkoxy group, an acylgroup, an acyloxy group, a halo group, an ether group or a polyethergroup.

In another aspect, a composition is provided that comprises a) a polymercomprising a first pendant group selected from at least oneperfluorinated ether group or perfluoroalkanesulfonamido group, a secondpendant group comprising an ammonium group, wherein the second pendantgroup is free of silicon, and a third pendant group comprising anammonium group and a reactive silicon-containing group, and b) at leastone water-soluble organic solvent or water.

In yet another aspect, a method of protecting a substrate is provided,the method comprising providing a composition comprising a polymer andat least one water-soluble organic solvent or water, and contacting thesubstrate with the composition. The polymer has a first pendant groupselected from at least one perfluorinated ether group orperfluoroalkanesulfonamido group, a second pendant group comprising anammonium group, wherein the second pendant group is free of silicon, anda third pendant group comprising an ammonium group and a reactivesilicon-containing group.

In yet another aspect, an article is provided comprising a substrate anda polymer, wherein the polymer is in contact with at least a portion ofa surface of the substrate, the polymer comprising a first pendant groupselected from at least one perfluorinated ether group orperfluoroalkanesulfonamido group, a second pendant group comprising anammonium group, wherein the second pendant group is free of silicon, anda third pendant group comprising an ammonium group and a reactivesilicon-containing group.

This summary is not intended to describe each and every embodiment orimplementation of the present invention. Further embodiments, features,and advantages of the present invention will be apparent from thefollowing detailed description thereof and from the claims.

DETAILED DESCRIPTION

In several places throughout the application, guidance is providedthrough lists of examples, which examples can be used in variouscombinations. In each instance, the recited list serves only as arepresentative group and should not be interpreted as an exclusive list.

Any recitation of numerical ranges by endpoints includes all numberssubsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3,3.80, 4, 5, etc.);

The terms “a,” “an,” “the,” “at least one,” and “one or more” are usedinterchangeably. Thus, for example, a composition that comprises “a”monomer of Formula I can be interpreted to mean that the compositionincludes “one or more” monomers of Formula I.

The term “(meth)acrylate” refers to either an acrylic acid ester, amethacrylic acid ester, or a combination of an acrylic acid ester and amethacrylic acid ester.

The term “ammonium group” refers to a group comprising a quaternarynitrogen atom (including a group having four single bonds to a nitrogenatom).

The term “reactive silicon-containing group” refers to a groupcomprising at least one silicon atom bonded to at least one of a hydroxygroup or group bonded to the silicon atom by a bond that ishydrolyzable.

The term “quaternizing agent” refers to a compound or compositioncapable of reacting with an amine group to form an ammonium group.

The term “silicon-free alkylating agent” refers to a compound orcomposition, free of silicon, capable of reacting with an amine group toform a new chemical bond between the amine nitrogen atom and a carbonatom in the alkylating agent.

A polymer is provided that comprises a first pendant group selected fromat least one perfluorinated ether group or perfluoroalkanesulfonamidogroup, a second pendant group comprising an ammonium group, where thesecond pendant group is free of silicon, and a third pendant groupcomprising an ammonium group and a reactive silicon-containing group.

The first pendant group is selected from at least one perfluorinatedether group or perfluoroalkanesulfonamido group. The perfluorinatedether group comprises at least one oxygen atom. The perfluorinated ethergroup can be a linear perfluorinated ether group, or it can comprisebranched or cyclic structures. An oxygen atom in the perfluorinatedether group can be in one or more of a linear, branched, or cyclicstructure. The perfluorinated ether group can have a weight averagemolecular weight (in units of grams per mole) of at least 200, at least300, at least 400, at least 500, at least 600, at least 700, at least800 at least 900, at least 1000, at least 1250, at least 1500, at least1750, at least 2000, at least 2250, at least 2500, at least 2750, atleast 3000, at least 3250, at least 3500, at least 3750, at least 4000,at least 4500, at least 5000, at least 5500, or at least 6000. Theperfluorinated ether group can have a weight average molecular weight ofnot greater than 6000, not greater than 5500, not greater than 5000, notgreater than 4500 not greater than 4000, not greater than 3500, notgreater than 3000, not greater than 2750, not greater than 2500, notgreater than 2250, not greater than 2000, not greater than 1750, notgreater than 1500, not greater than 1250, not greater than 1000, notgreater than 900, not greater than 800, not greater than 700, notgreater than 600, not greater than 500, not greater than 400, notgreater than 300, or not greater than 200. The perfluorinated ethergroup can have a weight average molecular weight of 200 to 6000, 300 to6000, 300 to 5000, 500 to 5000, 750 to 5000, 750 to 4500, 1000 to 4500,1250 to 4500, 1250 to 4000, 1250 to 3750, 1250 to 3500, 1250 to 3250,1250 to 3200, or 1250 to 3000.

The perfluorinated ether group can comprise a perfluoroalkyl group, aperfluoroalkylene group, or both. The perfluoroalkyl group can compriseone or more of a linear, branched, or cyclic structure. Non limitingexamples of perfluoroalkyl groups include perfluoromethyl,perfluoroethyl, perfluoropropyl, perfluorobutyl, perfluoro-2-butyl,perfluorohexyl, perfluorocyclohexyl, and perfluorocyclohexylmethylgroups. The perfluoroalkylene group can comprise one or more of alinear, branched, or cyclic structure. Non limiting examples ofperfluoroalkylene groups include perfluoromethylene, perfluoroethylene,and perfluoro-1,2-propylene.

The perfluorinated ether group can be derived from, for example,tetrafluoroethylene or hexafluoropropylene, as described in, forexample, U.S. Pat. No. 3,882,193 (Rice et al.) and U.S. Pat. No.3,250,807 (Fritz et al.). The perfluorinated ether group can be derivedfrom, for example, hexafluoropropylene oxide, as described in, forexample, U.S. Pat. No. 6,923,921 (Flynn et al.) and U.S. Pat. No.3,250,808 (Moore, Jr. et al.).

In some embodiments, the perfluorinated ether group is aperfluoropolyether group. The perfluoropolyether group comprises atleast two oxygen atoms, and can comprise more than two oxygen atoms.

The perfluorinated ether group can comprise a structure of Formula IVF(C_(m)F_(2m)O)_(n)C_(p)F_(2p)—,  (IV)wherein m is an integer of 1 to 12, n is an integer of 1 to 40, and p isan integer of 1 to 6. In some embodiments, m is an integer of at least1, at least 2, at least 3, at least 4, at least 5, at least 6, at least7, at least 8, at least 9, at least 10, or at least 11. In someembodiments, m is an integer of 12, less than 12, less than 11, lessthan 10, less than 9, less than 8, less than 7, less than 6, less than5, less than 4, less than 3, or less than 2. In some embodiments, n isan integer of at least 1, at least 2, at least 4, at least 6, at least8, at least 10, at least 12, at least 14, at least 16, at least 18, atleast 20, at least 22, at least 24, at least 26, at least 28, at least30, at least 32, at least 34, at least 36, or at least 38. In someembodiments, n is an integer of 40, less than 40, less than 38, lessthan 36, less than 34, less than 32, less than 30, less than 28, lessthan 26, less than 24, less than 22, less than 20, less than 18, lessthan 16, less than 14, less than 12, less than 10, less than 8, lessthan 6, less than 4, or less than 2. In some embodiments, p is aninteger of 1, 2, 3, 4, 5, or 6. The substructures C_(m)F_(2m) andC_(p)F_(2p) can independently comprise one or more of a linear,branched, or cyclic structure. The preparation of perfluorinated etherscomprising such structures can result in a mixture of perfluorinatedethers, each comprising structures having different integer values of m,n, and p. Such mixtures of perfluorinated ethers can have non-integeraverage values of m, n, and p.

The perfluorinated ether group of Formula IV can comprise a structure ofFormula VIF(CF(CF₃)CF₂O)_(n)CF(CF₃)—,  VIwherein n is as defined above. The preparation of perfluorinated ethersof Formula VI can result in a mixture of perfluorinated ethers, eachcomprising structures having different integer values of n. Suchmixtures of perfluorinated ethers can have non-integer average values ofn.

The perfluoroalkanesulfonamido group has the structure of Formula VC_(x)F_(2x+1)SO₂N(R¹)—  (V)wherein x is an integer of 1 to 6 and R¹ is selected from a hydrogenatom, an alkyl group, an aryl group, and an aralkyl group. In Formula V,x can be an integer of 1, 2, 3, 4, 5, or 6. In Formula V, R¹ can be, forexample, a methyl group, an ethyl group, a propyl group, a butyl group,a phenyl group, or a benzyl group. The preparation ofperfluoroalkanesulfonamido compounds comprising such structures canresult in a mixture of compounds comprising a perfluoroalkanesulfonamidogroup, each comprising structures having different integer values of x.Such mixtures of compounds each comprising a perfluoroalkanesulfonamidogroup can have non-integer average values of x.

When R¹ in Formula V is an alkyl group, the alkyl group can be a linear,branched, or cyclic alkyl group. The alkyl group can comprise linear,branched, or cyclic structures. The alkyl group can comprise up to 20,up to 18, up to 16, up to 14, up to 12, up to 10, up to 8, up to 6, upto 4, up to 2 carbon atoms, or 1 carbon atom. The alkyl group cancomprise less than 20, less than 18, less than 16, less than 14, lessthan 12, less than 10, less than 8, less than 6, less than 4, or lessthan 2 carbon atoms. Non-limiting examples of alkyl groups includemethyl, ethyl, propyl, butyl, hexyl, octyl, decyl, 2-propyl, 2-butyl,2-hexyl, cyclohexyl, and cyclohexylmethyl. In some embodiments, R¹ is amethyl group. In other embodiments, R¹ is an ethyl group.

When R¹ in Formula V is an aryl group, the aryl group can comprise onearene ring or more than one arene ring. Aryl groups can comprise up to 6carbon atoms, up to 8 carbon atoms, up to 10 carbon atoms, up to 12carbon atoms, up to 14 carbon atoms, up to 16 carbon atoms, or up to 18carbon atoms. In some embodiments, aryl groups can comprise aheteroarene ring (i.e., an arene ring comprising a heteroatom, forexample, nitrogen, oxygen, or sulfur). If more than one arene ring ispresent in an aryl group, the arene rings (which can be the same ordifferent) can be fused together, or they can be joined by a chemicalbond. Non-limiting examples of aryl groups include substituted andunsubstituted phenyl, 1-naphthyl, 2-naphthyl, 9-anthracenyl, andbiphenyl. In some embodiments, R¹ is a phenyl group.

When R¹ in Formula V is an aralkyl group, the aralkyl group can compriseone arene ring or more than one arene ring. The aralkyl group cancomprise up to 6 carbon atoms, up to 8 carbon atoms, up to 10 carbonatoms, up to 12 carbon atoms, up to 14 carbon atoms, up to 16 carbonatoms, up to 18 carbon atoms, or up to 20 carbon atoms. If more than onearene ring is present in the aralkyl group, the arene rings (which canbe the same or different) can be fused together, or they can be joinedby a chemical bond. In some embodiments, aralkyl groups can comprise aheteroaralkyl group, i.e., comprising a heteroarene ring. The aralkylgroup comprises one or more alkyl groups. The alkyl groups can be bondedto an arene ring, and can comprise 1, 2, 3, 4, 5, 6, or more than 6carbon atoms. Examples of alkyl groups include methyl, ethyl, 1-propyl,2-propyl, 1-butyl, and 2-butyl groups. Non-limiting examples of aralkylgroups include benzyl, 4-methyl benzyl, 1-phenylethyl, 2-phenylethyl,3-phenylpropyl, 2-naphthylethyl, and 9-anthracenylmethyl.

Useful perfluoroalkanesulfonamido groups include, but are not limitedto, perfluorobutanesulfonamido groups having the FormulasC₄F₉SO₂N(CH₃)—, C₄F₉SO₂N(CH₂CH₃)—, C₄F₉SO₂N(CH₂CH₂CH₃)—, andC₄F₉SO₂N(CH₂CH₂CH₂CH₃)—.

The second pendant group comprises an ammonium group and is free ofsilicon. The ammonium group comprises the structure of Formula VII

wherein R² comprises at least one of an alkylene group, a heteroalkylenegroup, an arylene group, or an aralkylene group, and each R³ isindependently a hydrogen atom or an alkyl group.

In some embodiments, R² comprises an alkylene group. The alkylene groupcan comprise one or more of a linear, branched, or cyclic structure. Insome embodiments, R² comprises a heteroalkylene group, i.e., an alkylenegroup that comprises at least one heteroatom, e.g., oxygen, nitrogen, orsulfur. The alkylene or heteroalkylene group can comprise at least 1carbon atom, or up to 2, up to 3, up to 4, up to 5, up to 6, up to 7, upto 8, up to 9, up to 10, up to 14, up to 16, up to 18, or up to 20carbon atoms. The alkylene or heteroalkylene group can comprise lessthan 20, less than 18, less than 16, less than 14, less than 12, lessthan 10, less than 8, less than 6, less than 4, or less than 2 carbonatoms. Non-limiting examples of alkylene groups include methylene,ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene, 1,4-cyclohexylene,and 1,4-cyclohexyldimethylene.

In some embodiments, R² comprises an arylene group. The arylene groupcomprises one or more arene rings. When the arylene group comprises morethan one arene ring, the arene rings (which can be the same ordifferent) can be fused, joined by a covalent bond, or joined via, forexample, a joining group such as an alkylene group or a heteroatom suchas oxygen. In some embodiments, the arylene group comprises at least oneheteroarene ring. The arylene group can comprise at least 4 carbonatoms, or at least 5, at least 6, at least 10, or at least 14 carbonatoms. Non-limiting examples of arylene groups include phenyl,1-naphthyl, 2-naphthyl, 9-anthracenyl, furanyl, and thiophenyl.

In some embodiments, R² comprises an aralkylene group. The aralkylenegroup can comprise one or more arene rings. When the aralkylene groupcomprises more than one arene ring, the arene rings (which can be thesame or different) can be fused, joined by a covalent bond, or joinedvia, for example, a joining group such as an alkylene group or aheteroatom such as oxygen. The aralkylene group can comprise at leastone heteroatom, e.g., oxygen, nitrogen, or sulfur. The aralkylene groupcan comprise at least about 4 carbon atoms, or at least about 5, atleast about 6, at least about 10, or at least about 14 carbon atoms.

Each R³ is independently a hydrogen atom or an alkyl group. Typically,at least one R³ is an alkyl group, and more typically, more than one R³are independently alkyl groups. When more than one R³ are independentlyalkyl groups, the alkyl groups can be the same or different. The alkylgroup can comprise 1 carbon atom, more than 1 carbon atom, more than 2carbon atoms, more than 4 carbons atoms, more than 6 carbon atoms, morethan 8 carbon atoms, more than 10 carbon atoms, more than 12, more than14, more than 16 carbon atoms, or more than 20 carbon atoms. The alkylgroup can comprise 20, less than 20, less than 18, less than 16, lessthan 14, less than 12, less than 10, less than 8, less than 6, less than4, or less than 2 carbon atoms. In some embodiments, the alkyl groupcomprises 1 to 8 carbon atoms. In some embodiments, the alkyl groupcomprises a straight chain alkyl group. In other embodiments, the alkylgroup comprises a branched alkyl group. In still other embodiments, thealkyl group comprises a cyclic alkyl group. Non-limiting examples ofalkyl groups include methyl, ethyl, 1-propyl, iso-propyl, butyl,iso-butyl, sec-butyl, pentyl, iso-pentyl, neo-pentyl, hexyl,2-ethylhexyl, octyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl,octadecyl, cyclohexyl, 4-methylcyclohexyl, cyclohexylmethyl, cyclopenyl,and cyclooctyl.

In some embodiments, R² comprises an alkylene group having from 1 to 6carbon atoms and each R³ is independently a hydrogen atom or an alkylgroup having from 1 to 4 carbon atoms. In some embodiments, R² comprisesan alkylene group having 2 carbon atoms, and more than one R³ are methylgroups.

The third pendant group comprises an ammonium group and a reactivesilicon-containing group. In some embodiments, the third pendant groupcomprises the structure of Formula VIII

where R⁴ and R⁶ independently comprise alkylene groups, arylene groups,or combinations thereof, each R⁵ is independently an alkyl group, andeach R⁷ is independently a hydroxy group or a group bonded to thesilicon atom via a hydrolyzable bond. In this context, “bonded to thesilicon atom via a hydrolyzable bond” refers to the reactivity of theR⁷-silicon bond with water (i.e., to a bond that is capable ofundergoing a hydrolysis reaction). In some embodiments, R⁷ is bonded tothe silicon atom via a bond including a carbon atom (i.e., R⁷ comprisesa carbon atom bonded to the silicon atom). In some embodiments, R⁷ isbonded to the silicon atom via a bond including an atom other than acarbon atom. In some embodiments, R⁷ is bonded to the silicon atom via abond including, for example, a nitrogen, oxygen, or sulfur atom (i.e.,R⁷ comprises a nitrogen, oxygen, or sulfur atom, respectively, bonded tothe silicon atom).

Each R⁷ can independently be a non-ionic group or an ionic group. Theionic group can be cationic, anionic, or zwitterionic. Non-limitingexamples of a non-ionic group include hydroxy, alkoxy, acyl, acyloxy,halo, ether, and polyether groups. Alkoxy groups include, for example,methoxy and ethoxy groups. Halo groups include, for example, chloro,bromo, and iodo groups. Acyl groups include, for example, acetyl,propionyl, and benzoyl groups. Acyloxy groups include, for example,acetoxy and propionoxy groups. Ether and polyether groups can compriseoxyalkylene groups, for example groups having the structure of FormulaIX

where v is an integer of 1 to 10 and w is an integer of 1 to 200. Anether group can include a group of Formula IX where w is 1. Non-limitingexamples of polyether groups comprising oxyalkylene groups includepoly(oxymethylene), poly(oxyethylene), and poly(oxybutylene) groups. InFormula IX, w can be an integer of at least 1, at least 2, at least 4,at least 6, at least 8, at least 10, at least 20, at least 30, at least40, at least 50, at least 60, at least 80, at least 100, at least 150,or at least 190. In Formula IX, w can be an integer of less than 200,less than 180, less than 160, less than 150, less than 140, less than120, less than 100, less than 80, less than 60, less than 40, less than20, less than 15, less than 10, less than 8, less than 6, less than 4,or less than 2. When R⁷ is an ionic group, it can be a cationic group,e.g., it can comprise a cationic nitrogen atom. Non-limiting examples ofionic groups include groups such as —OCH₂CH₂N⁺(CH₃)₃I⁻, —OCH₂CH₂N⁺ Cl⁻,and —OCH₂CH₂N⁺(CH₃)₂CH₂CH₂CH₂SO₃ ⁻. In some embodiments, polyethergroups comprising more than one oxyalkylene group further comprises acationic group (e.g., a group comprising a cationic nitrogen atom), ananionic group, or both a cationic group and an anionic group.

The alkylene group of Formula IX (i.e., the group having thesubstructure C_(v)H_(2v)) can independently comprise one or more of alinear, a branched, or a cyclic structure. In Formula IX, v can be 1, 2,3, 4, 5, 6, 7, 8, 9, or 10. Non-limiting examples of alkylene groupsinclude methylene, ethylene, 1,3-propylene, 1,2-propylene, 1,4-butylene,1,4-cyclhexylene, and 1,4-cyclohexyldimethylene.

In some embodiments, R⁴ and R⁶ independently comprise alkylene groupshaving from 1 to 6 carbon atoms, each R⁵ is independently an alkyl grouphaving from 1 to 4 carbon atoms, and each R⁷ is independently a hydroxygroup, an alkoxy group, an acyl group, an acyloxy group, a halo group,an ether group, or a polyether group. In some embodiments, each R⁷ isindependently a hydroxy group, a methoxy group, or an ethoxy group.

The polymer can further comprise a fourth pendant group. The fourthpendant group comprises a nonionic non-fluorinated group. Examples ofnonionic non-fluorinated groups include unsubstituted and substitutedalkyl groups having one or more of a linear, branched, or cyclicstructure, and aryl groups. The alkyl groups can be substituted with,for example, halogen (other than fluorine) or the alkyl groups cancontain, for example, an oxygen atom. Non-limiting examples of alkylgroups include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl,dodecyl, 2-propyl, 2-butyl, 2-hexyl, 2-octyl, 3-octyl, 4-octyl,2-ethylhexyl, 2-decyl, 4-decyl, 2-dodecyl, 3-dodecyl, cyclohexyl,cyclohexylmethyl, isobornyl, and cyclooctyl groups. The aryl groupsinclude groups comprising at least one arene ring, e.g., unsubstitutedand substituted arene rings. Non-limiting examples of such aryl groupsinclude phenyl, 2-methylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl,benzyl, 4-methylbenzyl, 1-naphthyl, and 2-naphthyl.

The polymer can be, for example, a vinyl ether polymer, a vinyl esterpolymer, a (meth)acrylamide polymer, or a (meth)acrylate polymer.Typically, the polymer is a (meth)acrylate polymer comprising a firstpendant group selected from at least one perfluorinated ether group orperfluoroalkanesulfonamido group, a second pendant group comprising anammonium group, where the second pendant group is free of silicon, and athird pendant group comprising an ammonium group and a reactivesilicon-containing group.

A polymer is provided, prepared from reactants comprising a firstmonomer having the structure of Formula I

a second monomer having the structure of Formula II

a first quaternizing agent comprising at least one of an acid or asilicon-free alkylating agent, and a second quaternizing agentcomprising the structure of Formula IIIX—R⁶Si(R⁷)₃  (III)where R_(f), R², R³, R⁶, and R⁷ are as described above.

In Formula I, the group A is a linking group having less than 11 carbonatoms. The linking group A can have 10 carbon atoms, 9 carbon atoms, 8carbon atoms, 7 carbon atoms, 6 carbon atoms, 5 carbon atoms, 4 carbonatoms, 3 carbon atoms, 2 carbon atoms, or 1 carbon atom. Linking group Acan comprise an alkylene group (e.g., an ethylene, propylene, orbutylene group), an arylene group (e.g., a phenylene group), or both.

The groups R¹⁰ and R¹¹ are independently a hydrogen atom or an alkylgroup having 1 to 4 carbon atoms.

In Formula III, the group X is a leaving group. The group X can be agroup such as the conjugate base of a strong acid, for example selectedfrom halo, alkyl sulfonate, fluorinated alkyl sulfonate, aryl sulfonate,and fluorinated aryl sulfonate.

In some embodiments, the polymer is substantially free of amino groups(i.e., substantially free of primary, secondary, or tertiary aminogroups). The term “substantially free of primary, secondary, or tertiaryamino groups” means that the polymer comprises less than 5 mole percent,less than 4 mole percent, less than 3 mole percent, less than 2 molepercent, less than 1 mole percent, less than 0.5 mole percent, less than0.25 mole percent, less than 0.15 mole percent, less than 0.1 molepercent, less than 0.075 mole percent, less than 0.05 mole percent, lessthan 0.025 mole percent, less than 0.02 mole percent, less than 0.015mole percent, less than 0.01 mole percent, less than 0.0075 molepercent, less than 0.005 mole percent, less than 0.0025 mole percent,less than 0.002 mole percent, less than 0.0015 mole percent, less than0.001 mole percent, less than 0.00075 mole percent, less than 0.0005mole percent, less than 0.00025 mole percent, less than 0.0002 molepercent, less than 0.00015 mole percent, less than 0.0001 mole percent,less than 0.000075 mole percent, less than 0.00005 mole percent, lessthan 0.000025 mole percent, less than 0.00002 mole percent, less than0.000015 mole percent, or less than less than 0.00001 mole percentprimary, secondary, or tertiary amino groups. In some embodiments, thepolymer is free of primary, secondary, or tertiary amino groups.

In some embodiments, the first quaternizing agent comprises an acid. Theacid can be an inorganic acid (e.g., a mineral acid) or an organic acid,or a mixture of an inorganic acid and an organic acid. Examples ofuseful acids include hydrochloric acid, hydrobromic acid, nitric acid,formic acid, acetic acid, propionic acid, maleic acid, fumaric acid, andbenzoic acid.

In some embodiments, the first quaternizing agent comprises asilicon-free alkylating agent. The silicon-free alkylating agent can beany silicon-free alkylating agent, i.e., any agent capable of reactingwith an amino group to produce an alkylated amino group. Classes ofsilicon-free alkylating agents include, for example, alkyl halides andaralkyl halides. Examples of useful silicon-free alkylating agentsinclude methyl iodide, ethyl chloride, butyl bromide, and benzylbromide.

In some embodiments, the second quaternizing agent comprises thestructure of Formula III wherein X is a chloro group, R⁶ is an alkylenegroup selected from ethylene, propylene, or butylene, and R⁷ is selectedfrom hydroxy, methoxy, or ethoxy.

The relative percentages of first and second quaternizing agents canvary over a wide range. Of the total of the first and secondquaternizing agents, the first quaternizing agent can comprise at least0.01 mole percent, at least 0.05 mole percent, at least 0.1 molepercent, at least 0.2 mole percent, at least 0.5 mole percent, at least1 mole percent, at least 2 mole percent, at least 5 mole percent, atleast 10 mole percent, at least 20 mole percent, at least 30 molepercent, at least 40 mole percent, at least 50 mole percent, at least 60mole percent, at least 70 mole percent, at least 80 mole percent, atleast 90 mole percent, at least 95 mole percent, at least 98 molepercent, at least 99 mole percent, at least 99.5 mole percent, at least99.9 mole percent, or at least 99.99 mole percent. Of the total of thefirst and second quaternizing agents, the first quaternizing agent cancomprise less than 0.01 mole percent, less than 0.05 mole percent, lessthan 0.1 mole percent, less than 0.2 mole percent, less than 0.5 molepercent, less than 1 mole percent, less than 2 mole percent, less than 5mole percent, less than 10 mole percent, less than 20 mole percent, lessthan 30 mole percent, less than 40 mole percent, less than 50 molepercent, less than 60 mole percent, less than 70 mole percent, less than80 mole percent, less than 90 mole percent, less than 95 mole percent,less than 98 mole percent, less than 99 mole percent, less than 99.5mole percent, or less than 99.9 mole percent.

In addition to the monomers of Formula I and Formula II, as describedabove, the polymer can be prepared from reactants further comprising athird monomer of Formula X

wherein R¹² is a hydrogen atom or an alkyl group having 1 to 4 carbonatoms, and R¹³ is a nonionic, non-fluorinated group. In someembodiments, R¹² is a hydrogen atom or a methyl group, and R¹³ is anunsubstituted or substituted alkyl group or an unsubstituted orsubstituted aryl group.

Typically, the first pendant group is derived from the first monomer ofFormula I, the second pendant group is independently derived from areaction of the second monomer of Formula II with a first quaternizingagent to provide a partially quaternized monomer, the third pendantgroup is derived from a reaction of a polymer product of the monomer ofFormula I and the partially quaternized monomer with a secondquaternizing agent, and the fourth pendant group, if present, is derivedfrom the third monomer of Formula X.

The polymer may be prepared from reactants further comprising a chaintransfer agent. For example, the chain transfer agent can comprise asulfur atom. In some embodiments, the chain transfer agent comprises athiol group. The chain transfer agent may have the structure Q—SR^(a),where Q comprises an alkyl group, an aryl group, an aralkyl group, areactive silicon-containing group, or combinations thereof, and R^(a) isselected from a hydrogen atom, an alkyl group, an aryl group, an aralkylgroup, and an acyl group. When Q and R^(a) are each an alkyl group, anaryl group, an aralkyl group, or a reactive silicon-containing group, Qand Ra can be the same or different. When Q or R^(a) is an alkyl group,Q or R^(a) may comprise about 1 to about 20 carbon atoms and maycomprise at least linear, branched, or cyclic structure. In someembodiments, the alkyl group comprises 1, 2, 3, 4, 5, 6, 7, 8, 9, 10,11, 12, 13, 14, 15, 16, 17, 18, 19, or 20 carbon atoms. When Q or R^(a)is an aryl group, Q or R^(a) may comprise about 4 to about 16 carbonatoms. When Q or R^(a) is an aralkyl group, Q or R^(a) may compriseabout 4 to about 20 carbon atoms. Typically, R^(a) is a hydrogen atom,an alkyl group having 1 to 7 carbon atoms, or an acyl group.

In some embodiments, Q comprises a reactive silicon-containing grouphaving the structure of Formula XI—R⁸Si(R⁹)₃  (XI)where R⁸ comprises an alkylene group, an arylene group, or both, andeach R⁹ is independently a hydroxy group or a group bonded to thesilicon atom via a hydrolyzable bond. In some embodiments, R⁸ is analkylene group having from 1 to 6 carbon atoms, and each R⁹ isindependently a hydroxy group, an alkoxy group, an acyl group, anacyloxy group, a halo group, an ether group, or a polyether group. Insome embodiments, R⁸ is an alkylene group having from 2 to 4 carbonatoms, and each R⁹ is independently a hydroxy group, a methoxy group, oran ethoxy group.

Representative chain transfer agents include octanethiol, decanethiol,dodecanethiol, (3-mercaptopropyl)trimethoxysilane, and(3-mercaptopropyl)triethoxysilane. The polymer can be prepared from anamount (e.g., a weight percentage) of chain transfer agent sufficient toprovide a polymer of a desired weight average molecular weight.

The polymer can be prepared from a reaction mixture comprising 0.01 to90 weight percent of a first monomer of Formula I and 0.01 to 50 weightpercent of a second monomer of Formula II (or the reaction product ofthe monomer of Formula II with one or both of the first quaternizingagent or the second quaternizing agent), based on the total weight ofthe monomers in the reaction mixture. The polymer can be prepared from areaction mixture comprising at least 0.1 weight percent, at least 0.5weight percent, at least 1 weight percent, at least 5 weight percent, atleast 10 weight percent, at least 20 weight percent, at least 30 weightpercent, at least 40 weight percent, at least 50 weight percent, atleast 60 weight percent, at least 70 weight percent, at least 80 weightpercent, at least 85 weight percent, at least 87 weight percent, atleast 89 weight percent, at least 89.5 weight percent, or at least 89.9weight percent of a first monomer of Formula I, based on the totalweight of the monomers in the reaction mixture. The polymer can beprepared from a reaction mixture comprising 90 weight percent, less than90 weight percent, less than 89.5 weight percent, less than 89 weightpercent, less than 85 weight percent, less than 80 weight percent, lessthan 70 weight percent, less than 60 weight percent, less than 50 weightpercent, less than 40 weight percent, less than 30 weight percent, lessthan 20 weight percent, less than 15 weight percent, less than 10 weightpercent, less than 5 weight percent, less than 1 weight percent, or lessthan 0.1 weight percent of a first monomer of Formula I, based on thetotal weight of the monomers in the reaction mixture.

In some embodiments, the polymer is prepared from a reaction mixturecomprising at least 0.1 weight percent, at least 0.5 weight percent, atleast 1 weight percent, at least 5 weight percent, at least 10 weightpercent, at least 15 weight percent, at least 20 weight percent, atleast 25 weight percent, at least 30 weight percent, at least 35 weightpercent, at least 40 weight percent, at least 45 weight percent, or atleast 49 weight percent, at least 49.5 weight percent, or at least 49.9weight percent of a second monomer of Formula II (or the reactionproduct of the monomer of Formula II with one or both of the firstquaternizing agent or the second quaternizing agent). In someembodiments, the polymer is prepared from a reaction mixture comprising50 weight percent, less than 50 weight percent, less than 49.9 weightpercent, less than 49.5 weight percent, less than 49 weight percent,less than 45 weight percent, less than 40 weight percent, less than 35weight percent, less than 30 weight percent, less than 25 weightpercent, less than 20 weight percent, less than 15 weight percent, lessthan 10 weight percent, less than 5 weight percent, less than 2 weightpercent of a second monomer of Formula II (or the reaction product ofthe monomer of Formula II with one or both of the first quaternizingagent or the second quaternizing agent).

In some embodiments, the polymer is prepared from a reaction mixturecomprising at least 0.1 weight percent, at least 0.5 weight percent, atleast 1 weight percent, at least 5 weight percent, at least 10 weightpercent, at least 15 weight percent, at least 20 weight percent, atleast 25 weight percent, at least 30 weight percent, at least 35 weightpercent, at least 40 weight percent, at least 45 weight percent, or atleast 49 weight percent, at least 49.5 weight percent, or at least 49.9weight percent of a third monomer of Formula X. In some embodiments, thepolymer is prepared from a reaction mixture comprising 50 weightpercent, less than 50 weight percent, less than 49.9 weight percent,less than 49.5 weight percent, less than 49 weight percent, less than 45weight percent, less than 40 weight percent, less than 35 weightpercent, less than 30 weight percent, less than 25 weight percent, lessthan 20 weight percent, less than 15 weight percent, less than 10 weightpercent, less than 5 weight percent, less than 2 weight percent, lessthan 1 weight percent, less than 0.5 weight percent, less than 0.25weight percent, less than 0.2 weight percent, or less than 0.1 weightpercent of a third monomer of Formula X.

The polymer can be prepared by a polymerization reaction of a reactionmixture comprising a first monomer of Formula I with a second monomer ofFormula II (and with a third monomer of Formula X, if present) to form aprecursor polymer, and then by reacting the resultant precursor polymerwith the first and second quaternizing agents. If the first quaternizingagent is an acid, the acid is typically reacted with the precursorpolymer before the second quaternizing agent is reacted. Alternatively,the polymer of the present invention can be prepared by first reacting asecond monomer of Formula II with a first quaternizing agent to form anintermediate ammonium product, then polymerizing the intermediateammonium product with a first monomer of Formula I (and a third monomerof Formula X, if present) to form an intermediate ammonium polymer. Thesecond quaternizing agent can then be reacted with the intermediateammonium polymer to provide a polymer.

Typically, the polymerization reaction is carried out with the use of athermal free radical initiator such as a peroxide (e.g., benzoylperoxide) or an azo compound (e.g., 2,2′-azobisisobutyronitrile).Alternatively, the reaction can be carried out with the use of aphotochemical radical initiator system that can include a photochemicalinitiator, and optionally at least one of a sensitizer, and an electrondonor compound.

The polymer comprises ammonium groups. The polymer further comprises ananion. The anion can be inorganic (e.g., chloride) or organic (e.g.,aceate). The composition and polymer of the present invention cancomprise more than one anion, for example chloride and acetate ions. Theanion can be derived from the first and second quaternizing agents, orit can be derived from, for example, an anion exchange reaction whereinan initial anion is exchanged for another anion.

The polymer is typically a linear polymer. The polymer can compriselinear, branched, or cyclic structures, or a combination of any oflinear, branched, or cyclic structures. In some embodiments, the polymeris a random polymer.

The polymer can have any weight average molecular weight. In someembodiments, the polymer can have a weight average molecular weight ofnot greater than 500,000, not greater than 400,000, not greater than300,000, not greater than 200,000, not greater than 100,000, not greaterthan 80,000, not greater than 60,000, not greater than 50,000, notgreater than 40,000, not greater than 30,000, not greater than 20,000,not greater than 15,000, not greater than 10,000, not greater than8,000, not greater than 6,000, not greater than 4,000, not greater than2,000, or not greater than 1,000. In some embodiments, the polymer has aweight average molecular weight of at least 1000, at least 2000, atleast 3000, at least 4000, at least 5000, at least 6000, at least 7000,at least 8000, at least 9000, at least 10,000, at least 12,000, at least15,000, at least 17,000, at least 20,000, at least 25,000, at least30,000, at least 40,000, at least 50,000, at least 60,000, at least70,000, at least 80,000, at least 90,000, at least 100,000, at least200,000, at least 300,000, at least 400,000 or at least 500,000.

In some embodiments, the polymer can be dissolved in a water-solubleorganic solvent. Typically, the polymer is prepared in a water-solubleorganic solvent. In some embodiments, the polymer can be dispersed inwater. In other embodiments, the polymer can be dissolved in water.Typically, the polymer can be dispersed in a mixture of water and awater-soluble organic solvent. In some embodiments, a solution or adispersion of the polymer in a solvent comprising a water-solubleorganic solvent is combined or diluted with water to provide a solutionor a dispersion of the polymer in a mixture of the solvent and water.

The composition can comprise at least one water-soluble organic solvent.The composition can comprise less than 10 weight percent to more than 99weight percent water-soluble organic solvent. The composition cancomprise more than 0.1 weight percent, more than 0.5 weight percent,more than 1 weight percent, more than 5 weight percent, more than 10weight percent, more than 20 weight percent, more than 30 weightpercent, more than 40 weight percent, more than 50 weight percent, morethan 60 weight percent, more than 70 weight percent, more than 80 weightpercent, more than 90 weight percent, or more than 99 weight percentwater-soluble organic solvent. The composition can comprise less than99.9 weight percent, less than 99.5 weight percent, less than 99 weightpercent, less than 95 weight percent, less than 90 weight percent, lessthan 80 weight percent, less than 70 weight percent, less than 60 weightpercent, less than 50 weight percent, less than 40 weight percent, lessthan 30 weight percent, less than 20 weight percent, or less than 10weight percent water-soluble organic solvent. The composition can beprovided as a concentrate in a water-soluble organic solvent.

The water-soluble organic solvent can be soluble in water in allproportions of organic solvent and water. The water-soluble organicsolvent can be soluble in water up to 1 weight percent, up to 2 weightpercent, up to 5 weight percent, up to 10 weight percent, up to, 20weight percent, up to 30 weight percent, up to 40 weight percent, up to50 weight percent, up to 60 weight percent, up to 70 weight percent, upto 80 weight percent, or up to 90 weight percent organic solvent inwater. The water-soluble organic solvent can be soluble in water up tomore than about 90 weight percent organic solvent in water. Suitableorganic solvents include ketones (e.g., acetone), ethers (e.g.,dimethoxyethane, tetrahydrofuran), esters (e.g., methyl acetate),carbonates (e.g., propylene carbonate), amides (e.g.,dimethylacetamide), sulfoxides (e.g., dimethylsulfoxide), sulfones(e.g., sulfolane), and alcohols (e.g., ethanol, isopropanol, n-propanol,methoxypropanol, dipropyleneglycol monomethyl ether). In someembodiments, the water-soluble organic solvent comprises a solvent usedto prepare the polymer. In some embodiments, the water-soluble organicsolvent comprises a solvent not used to prepare the polymer, for examplea solvent that is added to the composition. In some embodiments, thewater-soluble organic solvent can be added to the composition during aprocessing or formulation step, for example during a solvent exchangeprocess.

The composition can comprise water. Water can be present from less thanabout 1 to more than about 99 weight percent of the composition. Thecomposition can comprise more than 0.1 weight percent, more than 0.5weight percent, more than 1 weight percent, more than 5 weight percent,more than 10 weight percent, more than 20 weight percent, more than 30weight percent, more than 40 weight percent, more than 50 weightpercent, more than 60 weight percent, more than 70 weight percent, morethan 80 weight percent, more than 90 weight percent, or more than 99weight percent water. The composition can comprise less than 99.9 weightpercent, less than 99.5 weight percent, less than 99 weight percent,less than 95 weight percent, less than 90 weight percent, less than 80weight percent, less than 70 weight percent, less than 60 weightpercent, less than 50 weight percent, less than 40 weight percent, lessthan 30 weight percent, less than 20 weight percent, less than 10 weightpercent, less than 5 weight percent, less than 1 weight percent, lessthan 0.5 weight percent, or less than 0.1 weight percent water.

The composition can comprise water and a water-soluble organic solvent.The percentage of water (of the total weight of water and awater-soluble organic solvent) can be less than 1 weight percent to morethan 99 weight percent. The percentage of water can be more than 1weight percent, more than 2 weight percent, more than 5 weight percent,more than 10 weight percent, more than 15 weight percent, more than 20weight percent, more than 30 weight percent, more than 40 weightpercent, more than 50 weight percent, more than 60 weight percent, morethan 70 weight percent, more than 80 weight percent, more than 90 weightpercent, more than 95 weight percent, more than 99 weight percent, morethan 99.5 weight percent, more than 99.8 weight percent, or more than99.9 weight percent of the total weight of water and a water-solubleorganic solvent. The percentage of water can be less than 99.9 weightpercent, less than 99.8 weight percent, less than 99.5 weight percent,less than 99 weight percent, less than 95 weight percent, less than 90weight percent, less than 85 weight percent, less than 80 weightpercent, less than 75 weight percent, less than 70 weight percent, lessthan 65 weight percent, less than 60 weight percent, less than 55 weightpercent, less than 50 weight percent, less than 45 weight percent, lessthan 40 weight percent, less than 35 weight percent, less than 30 weightpercent, less than 25 weight percent, less than 20 weight percent, lessthan 15 weight percent, less than 10 weight percent, less than 5 weightpercent, less than 2 weight percent, or less than 1 weight percent.

The concentration of the polymer in a mixture of water and a watersoluble organic solvent can be more than 1 weight percent, more than 2weight percent, more than 5 weight percent, more than 10 weight percent,more than 15 weight percent, more than 20 weight percent, more than 30weight percent, more than 40 weight percent, more than 50 weightpercent, more than 60 weight percent, more than 70 weight percent, morethan 80 weight percent, or more than 90 weight percent. Theconcentration of the polymer in a mixture of water and a water solubleorganic solvent can be less than 90 weight percent, less than 85 weightpercent, less than 80 weight percent, less than 75 weight percent, lessthan 70 weight percent, less than 65 weight percent, less than 60 weightpercent, less than 55 weight percent, less than 50 weight percent, lessthan 45 weight percent, less than 40 weight percent, less than 35 weightpercent, less than 30 weight percent, less than 25 weight percent, lessthan 20 weight percent, less than 15 weight percent, less than 10 weightpercent, less than 5 weight percent, less than 2 weight percent, lessthan 1 weight percent, less than 0.5 weight percent, less than 0.2weight percent, or less than 0.1 weight percent.

The compositions can comprise one or more additives. Such additives caninclude, for example, UV absorbers, inorganic or organic microparticlesor nanoparticles, buffering agents, fireproofing agents, antistaticagents, antimicrobial agents (e.g., fungicidal agents), sequesteringagents, mineral salts, surfactants, or bleaching agents.

Method and Article

A method of protecting a substrate is provided, the method comprisingproviding a composition comprising a) a polymer having a first pendantgroup selected from at least one perfluorinated ether group orperfluoroalkanesulfonamido group, a second pendant group comprising anammonium group, wherein the second pendant group is free of silicon, anda third pendant group comprising an ammonium group and a reactivesilicon-containing group, and b) at least one of a water-soluble organicsolvent or water. The method further comprises contacting the substratewith the composition. In some embodiments, the method comprisesproviding a composition comprising a polymer that further comprises afourth pendant group comprising a nonionic, non-fluorinated group. Insome embodiments, the polymer is substantially free of amino groups. Inother embodiments, the polymer is free of amino groups.

The step of contacting can comprise, for example, immersing a substratein a composition, condensing, spraying, brushing, or rolling thecomposition on a substrate, or flooding a substrate with a composition.The substrate can include textile, silicate, paper, metal, wood, andplastic. In some embodiments, the substrate can be cotton, viscose,wool, silk, polyester, polyamide, rayon, clay, ceramic, glass, concrete,and combinations thereof. In some embodiments, the method comprisescontacting a substrate with a composition comprising a polymer and atleast one of a water soluble organic solvent or water.

The substrate can comprise a ceramic. Such ceramic can be in the formof, for example, glazed or unglazed ceramic tile (e.g., kitchen orbathroom tile). The substrate can comprise glass, for example,fiberglass, flint glass or borosilicate glass. The substrate cancomprise concrete, including, but not limited to, structural concreteand decorative concrete. In some embodiments, the substrate can be atextile comprising a blend of cotton and polyester or a blend ofpolyamide and polyester. In some embodiments, the substrate comprises atextile suitable for use in clothing or upholstery.

The composition can be used to protect a substrate, particularly thesurface of a substrate, so as to render the substrate oil repellent,water repellent, or both, or to provide stain repellency to suchsubstrates. Protection of a substrate can result in rendering theprotected substrate, particularly the surface or protected surface of aprotected substrate, more readily cleanable due to the oil and/or waterrepellent nature of the protected substrate or surface. Typically, asubstrate is protected by an amount of a composition sufficient toresult in the substrate having a contact angle with distilled water ofat least 80° and a contact angle with hexadecane of at least 40°. Insome embodiments, the protected substrate can remain protected after theprotected substrate is subjected to abrasion or scrubbing.

The method of protecting a surface can comprise combining a composition,particularly a composition comprising a polymer and a water-solubleorganic solvent, with water to provide an aqueous mixture. A compositioncan be combined with water by adding water to the composition or byadding the composition to water. In some embodiments, combining acomposition with water comprises diluting a composition (in someembodiments comprising a water-soluble organic solvent) with water. Insome embodiments of the method, the step of providing a compositioncomprises combining the composition with water. Additives such as acidsor bases can be added to the aqueous mixture.

In some embodiments, a substrate, or particularly the surface of asubstrate, can be cleaned prior to contacting it with the composition.The substrate can be cleaned prior to contacting it with thecomposition, for example by washing the substrate with water or with anorganic solvent.

An article comprising a substrate and a polymer is provided. The polymeris in contact with at least a portion of a surface of the substrate, thepolymer comprising a first pendant group selected from at least oneperfluorinated ether group or perfluoroalkanesulfonamido group, a secondpendant group comprising an ammonium group, wherein the second pendantgroup is free of silicon, and a third pendant group comprising anammonium group and a reactive silicon-containing group. In someembodiments, the polymer further comprises a fourth pendant groupcomprising a nonionic, non-fluorinated group. In some embodiments, thepolymer is substantially free of amino groups. In other embodiments, thepolymer is free of amino groups. The substrate can include textile,silicate, paper, metal, wood, and plastic. In some embodiments, thesubstrate can be cotton, viscose, wool, silk, polyester, polyamide,rayon, clay, ceramic, glass, concrete, and combinations thereof.

EXAMPLES

Unless otherwise noted, all reagents and solvents can be obtained fromSigma-Aldrich Co., St. Louis, Mo.

“MeFSBEA” refers to the acrylic acid ester ofN-2-hydroxyethyl-N-methylperfluorobutanesulfonamide, preparedessentially as described in WO 01/30873.

“3-CPTES” refers to 3-chloropropyltriethoxysilane.

“DMAEMA” refers to N,N-dimethylaminoethyl methacrylate.

“HSPTES” refers to (3-mercaptopropyl)triethoxysilane.

“MAOPTES” refers to (3-methacryloxypropyl)triethoxysilane.

“AIBN” refers to 2,2′-azobisisobutyronitrile.

“HOAc” refers to acetic acid.

“HFPO acrylate” refers to a perfluoropolyether acrylate, the acrylicacid ester of an alcohol derived from an oligomer of hexafluoropropyleneoxide, the oligomer having a weight average molecular weight ofapproximately 1300, prepared as described in U.S. Pat. No. 6,923,921(Flynn, et al.).

Example 1 Preparation of a Polymer

A 500 mL 3-neck flask, fitted with a mechanical stirrer, a heatingmantle, a reflux condenser, and a thermometer, was charged with MeFBSEA(49.3 g), DMAEMA (13.3 g), HSPTES (4 g), isopropanol (73 g), and AIBN(0.15 g). The mixture was degassed by three cycles of partiallyevacuating the flask and refilling it with nitrogen gas. The mixture wasstirred under a nitrogen atmosphere and was heated to approximately 70°C. After approximately 6 hours, an additional 0.05 g of AIBN was added.The mixture was stirred at approximately 70° C. overnight, after whichtime 3-chloropropyltrimethoxysilane (21.6 g) was added to the flask. Thetemperature was increased to approximately 80° C. and the mixture wasstirred for an additional approximately 16 hours. The mixture wasallowed to cool to room temperature to afford the product as anapproximately 50 weight percent solution of a polymer in isopropanol.

Example 2 Preparation of a Polymer

A 500 mL 3-neck flask, fitted with a mechanical stirrer, a heatingmantle, a reflux condenser, and a thermometer was charged with MeFBSEA(49.3 g), DMAEMA (13.0 g), octanethiol (2.9 g), isopropanol (73 g), andAIBN (0.15 g). The mixture was degassed by three cycles of partiallyevacuating the flask and refilling it with nitrogen gas. The mixture wasstirred under a nitrogen atmosphere and was heated to approximately 70°C. After approximately 6 hours, an additional 0.05 g of AIBN was added.The mixture was stirred at approximately 70° C. overnight, after whichtime 3-CPTES (20.5 g) was added to the flask. The temperature wasincreased to approximately 80° C. and the mixture was stirred for anadditional approximately 16 hours. The mixture was allowed to cool toroom temperature to afford the product as an approximately 50 weightpercent solution of a polymer in isopropanol.

Example 3 Preparation of a Polymer

A 500 mL 3-neck flask, fitted with a mechanical stirrer, a heatingmantle, a reflux condenser, and a thermometer was charged with MeFBSEA(49.3 g), DMAEMA (7.9 g), HSPTES (4 g), isopropanol (73 g), and AIBN(0.15 g). The mixture was degassed by three cycles of partiallyevacuating the flask and refilling it with nitrogen gas. The mixture wasstirred under a nitrogen atmosphere and was heated to approximately 70°C. After approximately 6 hours, an additional 0.05 g of AIBN was added.The mixture was stirred at approximately 70° C. overnight, after whichtime 3-CPTES (12.5 g) was added to the flask. The temperature wasincreased to approximately 80° C. and the mixture was stirred for anadditional approximately 16 hours. The mixture was allowed to cool toroom temperature to afford the product as an approximately 50 weightpercent solution of a polymer in isopropanol.

Examples 4-9 Preparation of Polymer

The polymer solutions of Examples 4-9 were prepared according to theprocedure essentially as described in Example 3. The compositions aregiven in Table 1.

TABLE 1 Composition of Polymers of Examples 4-9. Example Wt. MeFBSEA Wt.DMAEMA Wt. HSPTES Wt. 3-CPTES 4 49.3 g 10.7 g 4.0 g 16.8 g 5 49.3 g 13.3g 4.0 g 20.9 g 6 49.3 g 16.0 g 4.0 g 25.1 g 7 49.3 g 26.6 g 5.9 g 41.8 g8 49.3 g 13.8 g 4.0 g 17.2 g 9 49.3 g  5.3 g 4.0 g  8.4 g

Example 10 Preparation of a Polymer

A 500 mL 3-neck flask, fitted with a mechanical stirrer, a heatingmantle, a reflux condenser, and a thermometer was charged with DMAEMA(10.7 g) and formic acid (0.8 g). To the stirring mixture there wasadded MeFBSEA (49.3 g), HSPTES (4 g), isopropanol (73 g), and AIBN (0.15g). The mixture was degassed by three cycles of partially evacuating theflask and refilling it with nitrogen gas. The mixture was stirred undera nitrogen atmosphere and was heated to approximately 70° C. Afterapproximately 6 hours, 0.05 g of AIBN was added. The mixture was stirredat approximately 70° C. overnight, after which time 3-CPTES (12.6 g) wasadded to the flask. The temperature was increased to approximately 80°C. and the mixture was stirred for an additional approximately 16 hours.The mixture was allowed to cool to room temperature to afford theproduct as an approximately 50 weight percent solution of a polymer inisopropanol.

Example 11 Preparation of a Polymer

The polymer solutions of Example 11 was prepared according to theprocedure essentially as described in Example 10, except that aceticacid (1.1 g) was used in place of formic acid, and 11.4 g of DMAEMA, 5.9g of HSPTES, and 13.0 g of 3-CPTES were added to the flask.

Examples 12-18 Preparation of Polymer

The polymer solutions of Examples 12-18 were prepared according to theprocedure essentially as described in Example 11. The compositions aregiven in Table 2.

TABLE 2 Composition of Polymers of Examples 12-18. Wt. Wt. Wt. Wt. Wt.Example MeFBSEA DMAEMA HOAc HSPTES 3-CPTES 12 49.3 g 11.4 g 3.2 g 5.9 g 4.3 g 13 49.3 g 10.7 g 1.0 g 4.0 g 12.6 g 14 49.3 g  7.9 g 1.0 g 4.0 g 8.2 g 15 49.3 g 10.7 g 3.2 g 4.0 g  4.2 g 16 49.3 g 10.7 g 2.1 g 4.0 g 8.4 g 17 49.3 g 10.7 g 0.9 g 4.0 g 10.9 g 18 49.3 g 11.0 g 1.1 g 4.0 g13.0 g

Example 19 Preparation of a Polymer

A 500 mL 3-neck flask, fitted with a mechanical stirrer, a heatingmantle, a reflux condenser, and a thermometer was charged with DMAEMA(14.4 g) and acetic acid (4.3 g). To the stirring mixture there wasadded HFPO acrylate (70.8 g), HSPTES (1.0 g), isopropanol (73 g), andAIBN (0.15 g). The mixture was degassed by three cycles of partiallyevacuating the flask and refilling it with nitrogen gas. The mixture wasstirred under a nitrogen atmosphere and was heated to approximately 70°C. After approximately 6 hours, an additional 0.05 g of AIBN was added.The mixture was stirred at approximately 70° C. overnight, after whichtime 3-CPTES (5.6 g) was added to the flask. The temperature wasincreased to approximately 80° C. and the mixture was stirred for anadditional approximately 16 hours. The mixture was allowed to cool toroom temperature to afford the product as an approximately 50 weightpercent solution of a polymer in isopropanol.

Examples 20-36 Protection of Ceramic Tile

Each product of Examples 1-8, 10, 11, and 13-19 (0.1 g each) was added,with stirring, to deionized water (98.9 g) to provide aqueous mixturesas dispersions or solutions. A 37 weight percent aqueous solution of HCl(1 g) was then added to each mixture to provide an aqueous spraymixture. White glazed ceramic tiles (available from Villeroy & Boch AG,Mettlach, Germany) were heated to approximately 100° C., and the glazedsides of separate tiles were sprayed with each aqueous spray mixture.The spray rate was approximately 40 mL of aqueous spray mixture perminute. Each tile was sprayed for approximately 30 seconds. The sprayedtiles were allowed to dry for approximately 24 hours. A portion thesprayed area of each tile was scrubbed, using an Erichsen cleaningmachine (obtained from DCI, Belgium) and a cleanser available under thetrade designation CIF CREAM (Unilever PLC, London, United Kingdom), for40 cycles to provide tiles with unscrubbed and scrubbed portions. Thestatic contact angle of each of water and hexadecane in the unscrubbedand scrubbed portions of each tile was measured using a Model DSA100contact angle measuring system (Kruss GmbH, Hamburg, Germany). The dataare given in Table 3.

TABLE 3 Ceramic Tile Contact Angle Data Contact angle Contact angle(unscrubbed) (scrubbed) Example Composition Water Hexadecane WaterHexadecane 20 Example 3   98° 61° 68° 46° 21 Example 4  103° 67° 70° 45°22 Example 5  104° 64° 65° 47° 23 Example 6  107° 67° 68° 48° 24 Example7   92° 58° 62° 41° 25 Example 1  102° 66° 65° 45° 26 Example 8  100°64° 69° 42° 27 Example 2  108° 67° 70° 48° 28 Example 11  99° 64° 64°46° 29 Example 13  97° 63° 62° 44° 30 Example 14 100° 65° 66° 46° 31Example 15  97° 62° 67° 47° 32 Example 16 103° 64° 66° 43° 33 Example 10 95° 66° 65° 48° 34 Example 17  98° 68° 67° 45° 35 Example 19 108° 70°63° 49° 36 Example 18 105° 60° 66° 42°

Examples 37-46 Protection of Glass

Each product of Examples 1, 3, 5, 6, 8, 11, 13, 15, 16, and 19 (0.1 geach) was added, with stirring, to deionized water (98.9 g) to provideaqueous mixtures as dispersions or solutions. A 37 weight percentaqueous solution of HCl (1 g) was then added to each mixture to providean aqueous spray mixture. Samples of window glass (10 cm×15 cm) weresprayed with each aqueous spray mixture. The spray rate wasapproximately 40 mL of aqueous spray mixture per minute. Each sample ofglass was sprayed for approximately 30 seconds. The sprayed glasssamples were allowed to dry for approximately 24 hours. A portion thesprayed area of each glass sample was scrubbed, using an Erichsencleaning machine (obtained from DCI, Belgium) and a sponge wet withdeionized water, for 4000 cycles to provide glass samples withunscrubbed and scrubbed portions. The static contact angle of each ofwater and hexadecane in the unscrubbed and scrubbed portions of eachglass sample was measured using a Model DSA100 contact angle measuringsystem (Kruss GmbH, Hamburg, Germany). The data are given in Table 4.

TABLE 4 Glass Contact Angle Data Contact angle Contact angle(unscrubbed) (scrubbed) Example Composition Water Hexadecane WaterHexadecane 37 Example 3   99° 69°  95° 60° 38 Example 5   95° 62°  88°56° 39 Example 6  103° 64° 100° 59° 40 Example 1  100° 63°  92° 55° 41Example 8   96° 66°  89° 55° 42 Example 11 102° 62°  99° 48° 43 Example13  95° 65°  81° 48° 44 Example 15  99° 66°  95° 54° 45 Example 16 100°63°  90° 54° 46 Example 19 102° 61°  93° 60°

Various modifications and alterations to this invention will becomeapparent to those skilled in the art without departing from the scopeand spirit of this invention. It should be understood that thisinvention is not intended to be unduly limited by the illustrativeembodiments and examples set forth herein and that such examples andembodiments are presented by way of example only with the scope of theinvention intended to be limited only by the claims set forth herein asfollows.

What is claimed is:
 1. A polymer prepared from reactants comprising: a)a first monomer having the structure of Formula I

b) a second monomer having the structure of Formula II

c) a first quaternizing agent comprising at least one of an acid or asilicon-free alkylating agent; and d) a second quaternizing agentcomprising the structure of Formula IIIX—R⁶—Si(R⁷)₃,  (III) wherein: R_(f) is selected from a structure ofFormula IV or Formula VF(C_(m)F_(2m)O)_(n)C_(p)F_(2p—)  (IV)C_(x)F_(2x+1)SO₂N(R¹)—,  (V) m is an integer of 1 to 12; n is an integerof 1 to 40; p is an integer of 1 to 6; x is an integer of 1 to 6; R¹ isa hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, andcombinations thereof; A is a linking group having less than 11 carbonatoms; R¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbonatoms; R² comprises at least one of an alkylene group, a heteroalkylenegroup, an arylene group, or an aralkylene group; each R³ isindependently a hydrogen atom or an alkyl group; R¹¹ is a hydrogen atomor an alkyl group having 1 to 4 carbon atoms; X is a leaving groupselected from the group consisting of halo, alkyl sulfonate, fluorinatedalkyl sulfonate, aryl sulfonate, and fluorinated aryl sulfonate; R⁶comprises an alkylene, an arylene group, or an aralkylene group; andeach R⁷ is independently selected from the group consisting of hydroxygroups, alkoxy groups, acyl groups, acyloxy groups, halo groups,polyether groups, and combinations thereof.
 2. A polymer prepared fromreactants comprising: a) a first monomer having the structure of FormulaI

b) a second monomer having the structure of Formula II

c) a first quaternizing agent comprising at least one of an acid or asilicon-free alkylating agent; and d) a second quaternizing agentcomprising the structure of Formula IIIX—R⁶—Si(R⁷)₃,  (III) wherein: R_(f) is selected from a structure ofFormula IV or Formula VF(C_(m)F_(2m)O)_(n)C_(p)F_(2p—)  (IV)C_(x)F_(2x+1)SO₂N(R¹)—,  (V) m is an integer of 1 to 12; n is an integerof 1 to 40; p is an integer of 1 to 6; x is an integer of 1 to 6; R¹ isa hydrogen atom, an alkyl group, an aryl group, or an aralkyl group, andcombinations thereof; A is a linking group having less than 11 carbonatoms; R¹⁰ is a hydrogen atom or an alkyl group having 1 to 4 carbonatoms; R² comprises at least one of an alkylene group, a heteroalkylenegroup, an arylene group, or an aralkylene group; each R³ isindependently a hydrogen atom or an alkyl group; R¹¹ is a hydrogen atomor an alkyl group having 1 to 4 carbon atoms; X is a leaving groupselected from the group consisting of halo, alkyl sulfonate, fluorinatedalkyl sulfonate, aryl sulfonate, and fluorinated aryl sulfonate; R⁶comprises an alkylene, an arylene group, or an aralkylene group; andeach R⁷ is independently selected from the group consisting of hydroxygroups, alkoxy groups, acyl groups, acyloxy groups, halo groups,polyether groups, and combinations thereof; wherein the polymer issubstantially free of amino groups.
 3. The polymer of claim 1 preparedfrom reactants further comprising a third monomer of Formula X:

wherein R¹² is a hydrogen atom or an alkyl group having 1 to 4 carbonatoms, and R¹³ is a nonionic, non-fluorinated group.
 4. The polymer ofclaim 1 prepared from reactants further comprising a chain transferagent.
 5. The polymer of claim 4 wherein the chain transfer agent hasthe structure Q—SR^(a), wherein Q comprises at least one of an alkylgroup, an aryl group, an aralkyl group, or a reactive silicon-containinggroup, and R^(a) is selected from a hydrogen atom, an alkyl group, anaryl group, an aralkyl group, and an acyl group.
 6. The polymer of claim5 wherein Q comprises the structure of Formula XI—R⁸Si(R⁹)₃,  (XI) wherein R⁸ comprises an alkylene group, an arylenegroup, or both, and each R⁹ is independently selected from the groupconsisting of hydroxy groups, alkoxy groups, acyl groups, acyloxygroups, halo groups, polyether groups, and combinations thereof.